The purpose of this study was to investigate the safety and efficacy of Rest-ZZZ, a natural sleep supplement, in healthy adults without a diagnosed sleep disorder. This randomized, double-blind, ...placebo-controlled, cross-over study consisted of three 7-day supplementation periods with either Rest-ZZZ, Diphenhydramine (DPH), or Placebo, with a 7-day washout. Twenty-seven participants were randomized to one of three intervention sequences and the Healthy People Sleep Quality Index (HPSQI), Quality of Life (QoL), and Profile of Mood States (POMS) questionnaires were assessed at the beginning and end of each supplementation period. Rest-ZZZ and Placebo showed improvements in sleep-related QoL (
p
≤ 0.044) and total mood disturbance (TMD) (
p
= ≤ 0.028). Fatigue–Inertia was reduced by all study products (
p
≤ 0.031). DPH did not result in any significant improvements on sleep quality parameters. A subgroup analysis of participants ≤ 45 years found enhanced efficacy of Rest-ZZZ and improvement in sleep-related QoL vs. Placebo (
p
= 0.007), as well as improvements in sleep duration (
p
= 0.007), sleep debt (
p
= 0.011), and sleep-related QoL (
p
= 0.033). DPH supplementation resulted in significant improvement in only sleep debt (
p
= 0.038). Rest-ZZZ had a safe hematology and chemistry profile. Rest-ZZZ resulted in restful sleep that generated corresponding improvements in sleep-related QoL and overall mood. Rest-ZZZ is an efficacious sleep supplement with a favorable safety profile, particularly in those aged 25–45 years.
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•59Co NMR of symmetrical and asymmetrical fac-Co(L-κS,O)3 acylthiourea complexes.•59Co chemical shifts highly sensitive to structure, temperature and solvent composition.•59Co NMR ...shows that all asymmetrical complexes are mixtures of EEE¸EEZ, ZZE and ZZZ configurational isomers.•Single crystal structure of fac-tris-(ZZE)-(N-methyl-N-phenyl-N′-benzoyl-thioureatocobalt(III)
A series of octahedral fac-Co(Ln-κS,O)3 complexes derived from symmetrical (RC(O)-NH–C(S)NR1R2; R = C6H5, R1, R2 = CH2CH3, (HL, n = 1–5)) and asymmetrical N,N-dialkyl-N′-acyl(aroyl)thioureas (RC(O)-NH-C(S)NR1R2; R = C6H5 or C(CH3)3, and R1 ≠ R2, (HL, n = 6–10)) were investigated by 1H, 13C and 59Co NMR in solution. The high receptivity of the 59Co nuclide (I = 7/2), and its large chemical shift range, is very sensitive to ligand structure, solvent composition and temperature. Relatively narrow 59Co NMR peaks and temperature coefficients in the range +2.16 and +3.0 ppm K−1 renders 59Co NMR a useful probe with which to study fac-Co(Ln-κS,O)3 complexes in solution. The formation of the previously unrecognized four possible EEE, EZZ, ZZZ and EEZ configurational isomers of fac-Co(L6-10-κS,O)3 complexes, derived from asymmetrical N,N-dialkyl-N′-acyl(aroyl)thioureas, is easily demonstrated by 59Co NMR. All analytically pure fac-Co(L6-10-κS,O)3 complexes are in fact mixtures of fac-EEE,EEZ,EZZ,ZZZ-Co(L6-10-κS,O) configurational isomers. Crystal structures of the symmetrical fac-tris-(N,N-diethyl-N′-4-methoxybenzoylthioureato)cobalt(III), and one configurational isomer of an asymmetrical fac-tris-(ZZE)-(N-methyl-N-phenyl-N′-benzoyl-thioureatocobalt(III), are reported.
In, pheromone extracts of calling female Chiasma clathrata, L. (Lepidoptera: Geometridae), a defoliator pest of alfalfa, (Z,Z,Z)-3,6,9–heptadecatriene and (Z,Z)-6,9–cis-3,4–epoxyhepta-decadiene was ...identified. Chiral gas chromatography using a modified cyclodextrin and synthetic reference samples proved the natural epoxide to show (3 R.4 S)-configuration. In field trapping tests, only the pure (3/R,4S)-enantiomer of the epoxide attracted males. The addition of the triene component was synergistic. Males of the sympatric species Tephrina arenaceciria Hbn. (Lepidoptera: Geometridae) were caught only in traps with baits containing the (3S,4R)-enantiomer together with a previously described minor component, (Z,Z)-3,9–cis-6,7–epoxyheptadecadiene, In trapping tests conducted iNADifferent biotope Abraxas grossu-lariata, L. (Lepidoptera: Geometridae) males were attracted by the (3S,4R)-enantiomer, whereas the (3/L4S)-enantiomer attracted a close relative. Abraxas sylvata Scop. (Lepidoptera: Geometridae). The present results suggest that one of the key mechanisms responsible for pheromone specificity among both the two alfalfa geometrids and the two Abraxas species in their respective biotops, may be the use of different enantiomers of the same polyene-derived epoxide as a sex pheromone component. It is probable that this discrimination mechanism is widespread among moth species utilizing epoxide pheromone components.